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作 者:任运来[1] 王文会[1] 田欣哲[1] 马军营[1] 任方平 李福伟[2]
机构地区:[1]河南科技大学化工与制药学院,河南洛阳471023 [2]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000
出 处:《分子催化》2016年第5期401-408,共8页Journal of Molecular Catalysis(China)
基 金:sponsored by the Open Project of State Key Laboratory for Oxo Synthesis and Selective Oxidation(Grant No.OSSO-2015-21);the Program for Science&Technology Innovation Talents in Universities of Henan Province(Grant No.15HASTIT004)
摘 要:这里发现锰化合物能够催化芳香碳-氧键的还原断裂.就我们所知,目前还没有锰催化芳香碳-氧键断裂方面的报道.以二苯并呋喃为底物,对各种反应条件进行优化,得到的较佳反应条件为5%Mn(OAc)_2,3当量LiAlH 4,140℃温度,四氢呋喃溶剂.在这个反应条件下,多种芳香碳-氧键能够发生还原断裂.甲醇钠的添加能够有效地促进二苯醚等底物的反应.对反应机理进行了初步研究,结果表明反应可能经历自由基过程.Manganese compounds were found to be effective to catalyze the reductive cleavage of carbon-oxygen bonds. To the best of our knowledge, no effective Mn-based catalyst was reported for this process. The reaction conditions were optimized by choosing dibenzofuran as the substrate, and the obtained optimum conditions were as follows: 5% Mn (OAc)2, 3 equiv. LiAlH4, 140℃ as the reaction temperature, THF as the solvent. The optimum conditions allowed a series of aromatic carbon-oxygen bonds to undergo the reductive cleavage. An addition of sodium methoxide was beneficial for the reaction of some substrates including diphenyl ethers. Preliminary mechanistic investigation suggests that the present reaction possibly undergoes a radical pathway.
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